EP0580559B1 - Verfahren zur Herstellung eines hochdispersen Platinteilchen enthaltenden Trägerkatalysators - Google Patents

Verfahren zur Herstellung eines hochdispersen Platinteilchen enthaltenden Trägerkatalysators Download PDF

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Publication number
EP0580559B1
EP0580559B1 EP93830295A EP93830295A EP0580559B1 EP 0580559 B1 EP0580559 B1 EP 0580559B1 EP 93830295 A EP93830295 A EP 93830295A EP 93830295 A EP93830295 A EP 93830295A EP 0580559 B1 EP0580559 B1 EP 0580559B1
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EP
European Patent Office
Prior art keywords
platinum
support
particles
catalyst
platinum particles
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP93830295A
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English (en)
French (fr)
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EP0580559A1 (de
Inventor
Tanaka Kikinzoku Kogyo Tech.Cen Tsurumi Kazunori
Paul Stonehart
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tanaka Kikinzoku Kogyo KK
Stonehart Associates Inc
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Tanaka Kikinzoku Kogyo KK
Stonehart Associates Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a process of preparing a catalyst which supports highly dispersed metal particles utilized in the field of catalysts.
  • Catalysts which support metals are widely utilized in various chemical reactions. Especially in the case of utilizing such an expensive catalyst as a precious metal, in order to effectively utilize the catalytically active metal, the particle diameter of the metal particles are required to be reduced as much as possible and to be uniformly supported on a support. Many attempts have been made especially for supporting metal particles having the minimum diameters on a support.
  • liberated colloid-like sulfur and a sulfate formed by the reaction of the above compound are contained.
  • the liberated sulfur which is a well-known catalytic poison against platinum strongly bonds the platinum to lower the catalytic performance.
  • the sulfate is non-volatile so that its removal should be conducted by water-washing.
  • the sulfate remained produces several inconveniences on the employment of the catalyst such as the existence as impurities and an undesired reaction with the support.
  • the liberated sulfur remained can be removed by thermal treatment in a hydrogen flow or in an oxidative flow, the heating may create the increase of the particle diameter by means of the agglomeration of the metal particles so that the desired particles cannot be obtained.
  • An object of the present invention is to provide a process of preparing a catalyst having monodispersed supported platinum particles.
  • Another object of the invention is to provide a process of preparing a catalyst having narrow particle size distribution and a particle diameter of less than about 2.0 nm (20 ⁇ ).
  • a further object of the present invention is to provide a process of preparing a catalyst having highly dispersed platinum particles without employing a sulfur-containing agent.
  • the catalyst supporting monodispersed platinum particles which has the narrow particle size distribution and of which a particle diameter is less than about 2.0 nm (20 ⁇ ) can be obtained by adding a support which supports platinum particles formed by reduction of a platinum-containing ion to a platinum-containing solution obtained by dissolving dinitrodiamine platinum in nitric acid under heating, adding thereto allyl alcohol arid hydrazine hydrate to form on the support a reaction product of the platinum-containing ion, the allyl alcohol and the hydrazine hydrate, and thermally treating the support in a reduction gas containing a hydrogen gas to reduce the reaction product to the platinum particles.
  • allyl alcohol and hydrazine hydrate are employed in place of a sulfur-containing agent for supporting the platinum particles on a support thereby avoiding the contamination of the sulfur component and the high temperature treatment for decomposing the sulfur-containing agent. Accordingly, the resulting catalyst contains no sulfur contaminant and substantially no agglomerated platinum particles.
  • a highly dispersed platinum-supported catalyst having a clean and active surface and the platinum particles of which a particle size is about less than 2.0 nm (20 ⁇ ) can be obtained. Further, the platinum containing rate of the resulting catalyst may reach nearly to 10 % in weight which is a target value of the platinum-supported catalyst.
  • Fig. 1 is a microphotograph of 1,000,000 magnifications of the platinum-supported carbon black catalyst obtained in Example 1 observed with a transmission electronic microscope.
  • Fig. 2 is a microphotograph of 1,000,000 magnifications of the catalyst in Comparative Example 2 which was obtained by treating the platinum-supported carbon black catalyst obtained in Comparative Example 1 in the hydrogen mixed flow at at 250 °C for one hour + at 350 °C for two hours observed with a transmission electronic microscope.
  • the reason why the allyl alcohol and the hydrazine hydrate are added to nitric acid solution of the dinitrodiamine platinum is that platinum-containing colloid is formed which is then supported on the support. If the allyl alcohol is added and then the hydrazine hydrate is added to the platinum solution prepared by dissolving the crystal of the dinitrodiamine platinum in the nitric acid without the addition of the catalyst support material, yellowish brown colloid-like particles are formed.
  • the platinum containing rate of the particles in this case is about 60 % in weight upon analysis. These particles are not platinum metal colloid and are considered to be a compound of the dinitrodiamine platinum, the allyl alcohol and the hydrazine hydrate though its structure is unknown.
  • the initial addition of the allyl alcohol and the hydrazine hydrate to the nitric acid solution of the dinitrodiamine platinum containing the support material enables to finely support the above compound on the support, and by thermally treating it in a hydron-containing flow, a catalyst which supports highly monodispersed platinum particles of which a particle diameter is less than about 2.0 nm (20 ⁇ ) can be obtained.
  • any material which is stable in a reduction atmosphere and in a reaction condition in which the resulting catalyst is employed can be utilized.
  • the most desirable support material is carbon black.
  • allyl alcohol and the hydrazine hydrate employed in the invention may removed by evaporation in the thermal treatment in the hydrogen-containing flow. Even if a small amount thereof remains, these do not contain any substance which acts as a catalytic poison so that the lowering of the catalytic performance is never expected.
  • This suspension was further stirred for two hours in a hot water bath of 50 °C so that the platinum-containing compound was completely supported on the carbon black.
  • the suspension containing the carbon black supporting the platinum-containing compound was filtered, the filtered solid was washed with 0.5 liter of pure water and dried at 60 °C for six hours.
  • the carbon black supporting the platinum-containing compound thus obtained was thermally treated in a hydrogen-nitrogen mixed flow containing 10 % of hydrogen at 250 °C for 30 minutes to obtain a platinum-supported carbon black catalyst.
  • the measurement of the platinum containing rate, the measurement of a specific surface area of the platinum and the observation of the state of the platinum particle dispersion by means of a transmission electronic microscope were conducted .
  • the platinum containing rate was 9.14 % in weight.
  • the specific surface area of the platinum was 163 m2/g which corresponds to a platinum particle having a diameter of 1.72 nm (17.2 ⁇ ) when converted into a spherical particle.
  • a microphotograph of 1,000,000 magnifications taken with a transmission electronic microscope is shown in Fig.1 which clarifies that the platinum particles of 1.0 to 2.0 nm (10 to 20 ⁇ ) are supported on the carbon black support under the monodispersed state.
  • the measurement of the platinum containing rate, the measurement of a specific surface area of the platinum and the observation of the state of the platinum particle dispersion by means of a transmission electronic microscope were conducted.
  • the platinum containing rate was 9.6 % in weight.
  • the specific surface area of the platinum was 16 m2/g which corresponds to a platinum particle having a diameter of 17.5 nm (175 ⁇ ) when converted into a spherical particle.
  • the particles of 1.0 to 2.0 nm (10 to 20 ⁇ ) were observed to be uniformly supported on the carbon black support, which was different from the result of the platinum surface area measured in accordance with the carbon monoxide adsorption.
  • the sulfur containing rate was measured by means of fluorescence X-rays. After this catalyst was treated in a hydrogen-nitrogen mixed flow of which hydrogen concentration was 50 % for one hour at 250 °C, the sulfur analysis, the measurement of a specific surface area of the platinum in accordance with the carbon monoxide adsorption and the observation with a transmission electronic microscope were conducted.
  • the catalyst after the above treatment with the hydrogen at 250 °C for one hour was further treated in a hydrogen-nitrogen mixed flow of which hydrogen concentration was 50 % for two hours at 350 °C, and the sulfur analysis, the measurement of a specific surface area of the platinum in accordance with the carbon monoxide adsorption and the observation with a transmission electronic microscope were conducted for the second time.
  • the results are shown in Table.
  • the sulfur component still remained even after the treatment in the hydrogen mixed flow at 250 °C for one hour + at 350 °C for two hours. Due to the contamination of the platinum surface with the sulfur, the platinum specific surface areas measured by means of the carbon monoxide adsorption are not in agreement with the particle sizes obtained through the observation with the transmission electronic microscope. This means the occurrence of the catalytic poisoning which lowered the catalytic activities.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Claims (1)

  1. Herstellungsverfahren eines Katalysators mit sehr dispergierten gelagerten Platinteilchen, das den Zusatz eines Trägers, der durch Reduktion eines platinenthaltenden Ions gebildete Platinteilchen trägt, zu einer durch Auflosen unter Heizung des Dinitrodiaminplatins in Salpetersäure erhaltenen platinenthaltenden Lösung, den darauffolgenden Zusatz von Allylalkohol und Hydrazinhydrat um ein Reaktionsprodukt des platinenthaltenden Ions, des Allylalkohols und des Hydrazinhydrats auf dem Träger zu bilden, und eine Wärmebehandlung des Trägers in einem wasserstoffenthaltenden Gas um das Reaktionsprodukt zu den Platinteilchen zu reduzieren umfasst.
EP93830295A 1992-07-06 1993-07-06 Verfahren zur Herstellung eines hochdispersen Platinteilchen enthaltenden Trägerkatalysators Expired - Lifetime EP0580559B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4202003A JPH0631166A (ja) 1992-07-06 1992-07-06 高分散白金微粒子担持触媒の製造方法
JP202003/92 1992-07-06

Publications (2)

Publication Number Publication Date
EP0580559A1 EP0580559A1 (de) 1994-01-26
EP0580559B1 true EP0580559B1 (de) 1995-12-20

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EP93830295A Expired - Lifetime EP0580559B1 (de) 1992-07-06 1993-07-06 Verfahren zur Herstellung eines hochdispersen Platinteilchen enthaltenden Trägerkatalysators

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US (1) US5350727A (de)
EP (1) EP0580559B1 (de)
JP (1) JPH0631166A (de)
DE (1) DE69301074T2 (de)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4443705A1 (de) * 1994-12-08 1996-06-13 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von tensidstabilisierten Mono- und Bimetallkolloiden der Gruppe VIII und Ib des Periodensystems als isolierbare und in hoher Konzentration wasserlösliche Precursor für Katalysatoren
DE4443701C1 (de) * 1994-12-08 1996-08-29 Degussa Schalenkatalysator, Verfahren zu seiner Herstellung und seine Verwendung
US5877128A (en) * 1996-04-26 1999-03-02 Platinum Research Organization Ltd. Catalyzed lubricant additives and catalyzed lubricant systems designed to accelerate the lubricant bonding reaction
US6258758B1 (en) 1996-04-26 2001-07-10 Platinum Research Organization Llc Catalyzed surface composition altering and surface coating formulations and methods
EP1007308B1 (de) 1997-02-24 2003-11-12 Superior Micropowders LLC Aerosolverfahren und -gerät, teilchenförmige produkte, und daraus hergestellte elektronische geräte
DE19710376A1 (de) * 1997-03-13 1998-09-17 Clariant Gmbh Katalysator zur hydrierenden Enthalogenierung von alpha-halogenierten Carbonsäuren sowie ein Verfahren zu seiner Herstellung
ITRM20020087A1 (it) * 2002-02-20 2002-05-21 Francesco Massimo De Catalizzatori di metalli nobili e non e loro leghe per pile a combustibile ottenuti mediante trattamento termico a bassa temperatura.
US20050053818A1 (en) * 2002-03-28 2005-03-10 Marc St-Arnaud Ion exchange composite material based on proton conductive functionalized inorganic support compounds in a polymer matrix
JP2005206931A (ja) 2003-12-26 2005-08-04 Sumitomo Electric Ind Ltd 金属粉末の製造方法
JP4571809B2 (ja) * 2004-02-05 2010-10-27 三菱レイヨン株式会社 貴金属含有触媒の製造方法
US8791056B2 (en) 2010-06-24 2014-07-29 Board Of Regents, The University Of Texas System Alkylphosphorofluoridothioates having low wear volume and methods for synthesizing and using same
US9725669B2 (en) 2012-05-07 2017-08-08 Board Of Regents, The University Of Texas System Synergistic mixtures of ionic liquids with other ionic liquids and/or with ashless thiophosphates for antiwear and/or friction reduction applications
JP6840056B2 (ja) * 2017-09-05 2021-03-10 Ｅｎｅｏｓ株式会社 脱水素触媒、水素の製造システム、及び水素の製造方法
JP7178127B1 (ja) * 2021-07-01 2022-11-25 石福金属興業株式会社 燃料電池用電極触媒の製造方法

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US3992512A (en) * 1971-06-16 1976-11-16 Prototech Company Finely particulated colloidal platinum compound and sol for producing the same, and method of preparation
JPS5127437B2 (de) * 1973-04-06 1976-08-12
US4137372A (en) * 1977-11-23 1979-01-30 United Technologies Corporation Catalyst and method for making
US4136059A (en) * 1977-12-12 1979-01-23 United Technologies Corporation Method for producing highly dispersed catalytic platinum
JPS5544375A (en) * 1978-09-27 1980-03-28 Agency Of Ind Science & Technol Dehydrogenation catalyst for alkyl substituted cyclohexane and dehydrogenation reaction method
WO1981002688A1 (en) * 1980-03-24 1981-10-01 Ytkemiska Inst A liquid suspension of particles of a metal belonging to the platinum group,and a method for the manufacture of such a suspension
FR2505205B1 (fr) * 1981-05-05 1986-05-23 Inst Francais Du Petrole Nouveaux catalyseurs de metaux nobles du groupe viii supportes a haute dispersion et grande activite leur fabrication et leur utilisation notamment dans les reactions d'hydrogenation

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US5350727A (en) 1994-09-27
JPH0631166A (ja) 1994-02-08
DE69301074D1 (de) 1996-02-01
EP0580559A1 (de) 1994-01-26
DE69301074T2 (de) 1996-06-20

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